MTBE and mixtures of branched C-8 hydrocarbons with gasoline blending properties similar to alkylate can be produced in a wide range of relative ratios and in an environmentally-friendly way by the simultaneous isobutene etherification/dimerization reaction. In the present paper thermodynamics and kinetics of the MTBE synthesis are presented as the theoretical background before discussing the experimental results for the new process obtained at laboratory scale, on pilot plant and on an industrial unit.